EP0036120B1 - Process for the production of bis-(amino-phenyl) disulphides - Google Patents
Process for the production of bis-(amino-phenyl) disulphides Download PDFInfo
- Publication number
- EP0036120B1 EP0036120B1 EP81101477A EP81101477A EP0036120B1 EP 0036120 B1 EP0036120 B1 EP 0036120B1 EP 81101477 A EP81101477 A EP 81101477A EP 81101477 A EP81101477 A EP 81101477A EP 0036120 B1 EP0036120 B1 EP 0036120B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- amino
- process according
- sulphur
- thiophenol
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
Definitions
- the invention relates to a process for the preparation of bis (aminophenyl) disulfides.
- Halogen is, for example, fluorine, chlorine, bromine, iodine, preferably chlorine or bromine, particularly preferably chlorine.
- Preferred amino-thiophenols for the process according to the invention are those in which R represents hydrogen or chlorine.
- Amino-thiophenols are known compounds and can be prepared by known processes, for example by reacting chloro-nitro-benzenes with hydrogen sulfides or sulfides (DE-OS 2 127 898).
- the amino-thiophenols are reacted with sulfur in the process according to the invention.
- the sulfur can be used in the form of elemental sulfur, such as sulfur powder, sulfur scales, sulfur flower, or via a sulfur-releasing substance in the process according to the invention. Gmelin's handbook of inorganic chemistry, 8th edition, volume 9, page 874 Verlag Chemie 1960).
- Sulfur or the sulfur-releasing substance is expediently used in the process according to the invention in an amount such that 0.4 to 0.7 mol, preferably 0.5 to 0.55 mol, of sulfur is present per mol of aminothiophenol.
- the process according to the invention is carried out at a temperature of 10 to 120 ° C., preferably 50 to 110 ° C. It is particularly preferred to work at the reflux temperature of the reaction mixture.
- the process according to the invention is generally carried out at a pressure between 0.01 and 1 bar, preferably 0.5 and 1 bar. Working at normal pressure is particularly preferred.
- the pH for carrying out the process according to the invention can be in the range from 3 to 9, preferably in the range from 4 to 8.
- salt-like sulfur-releasing substances such as sodium thiosulfate, and / or when using the aminothiophenols in the form of their salts
- the pH is adjusted by adding a small amount of a mineral acid or organic acid.
- amino-thiophenols are reacted with sulfur, the required pH is generally established without further auxiliaries.
- an acid used to adjust the pH
- a strong mineral acid such as hydrochloric acid or sulfuric acid
- a weak mineral acid such as e.g. B. carbonic acid (carbon dioxide in water) or an organic acid such as acetic acid or formic acid.
- the starting components are dispersed in water at room temperature and then heated to the reaction temperature with stirring, the hydrogen sulfide formed during the reaction escaping.
- the hydrogen sulfide is isolated or converted by customary methods, for example by absorption in alkali metal hydroxide solutions and conversion into the associated alkali metal salt or by oxidation to sulfur.
- a slight vacuum is applied to the reaction mixture or a carrier gas stream, for example nitrogen or air, is passed through the reaction mixture to largely remove the remaining hydrogen sulfide.
- the product can be isolated in a conventional manner, for example by filtration, suction or centrifuging.
- the bis (aminophenyl) disulfides are obtained by the process according to the invention in practically quantitative yields and in high purity, while the processes according to the prior art always produce more or less highly contaminated products.
- the bis- (aminophenyl) disulfides which can be prepared by the process according to the invention can be used as fungicides, mordants for epoxy resins, components for lubricating oil additives, components for polyurethane prepolymers, rubber peptizers and as intermediates for the synthesis of benzothiazole derivatives (DE-US 2 503 164).
- Example 2 The experiment is carried out as described in Example 2, with the difference that the pH is adjusted to 5 at about 80 ° C. by the dropwise addition of acetic acid.
- Example 2 The experiment is carried out as described in Example 2, with the difference that carbon dioxide is introduced at about 80 ° C. and the pH is adjusted to 5 by dropwise addition of 40% strength sulfuric acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Bis-(amino-phenyl)-disulfiden.The invention relates to a process for the preparation of bis (aminophenyl) disulfides.
Es ist bekannt, daß man Bis-(amino-phenyl)-disulfide erhält, wenn man 2-Nitro- oder 4-Nitro-chlorbenzol zunächst mit Natriumsulfid oder Natriumsulfid/Schwefel in Wasser umsetzt und dann mit Luftsauerstoff oder Wasserstoffperoxid oxidiert (US-PS 1 933 217; DE-OS 2 053 715). Es sind auch Varianten dieses Verfahrens bekannt geworden, bei denen ohne die genannten Oxidationsmittel gearbeitet wird (DE-OS 2503164; DE-OS 2758786; US-PS 3150186). Die nach diesen Herstellungsmethoden erhaltenen Produkte enthalten jedoch mehi oder weniger große Mengen an Verunreinigungen, so daß für verschiedene Verwendungszwecke verlustreiche Reinigungsprozesse erforderlich werden.It is known that bis (aminophenyl) disulfides are obtained if 2-nitro- or 4-nitro-chlorobenzene is first reacted with sodium sulfide or sodium sulfide / sulfur in water and then oxidized with atmospheric oxygen or hydrogen peroxide (US Pat 1 933 217; DE-OS 2 053 715). Variants of this method have also become known in which work is carried out without the oxidizing agents mentioned (DE-OS 2503164; DE-OS 2758786; US Pat. No. 3,150,186). However, the products obtained by these production methods contain more or less large amounts of impurities, so that lossy cleaning processes are required for various purposes.
Weiter ist bekannt, daß man Bis-(2-amino-phenyl)-disulfid erhält, wenn man 2-Amino-thiophenol oder sein Natriumsalz mit Dimethylsulfoxid oder mit Wasserstoffperoxid umsetzt (US-PS 3 981 809; US-PS 4 136 118). Dimethylsulfoxid und Wasserstoffperoxid sind jedoch, verglichen mit Luftsauerstoff und Schwefel, teure Oxidationsmittel.It is also known that bis (2-aminophenyl) disulfide is obtained if 2-amino-thiophenol or its sodium salt is reacted with dimethyl sulfoxide or with hydrogen peroxide (US Pat. No. 3,981,809; US Pat. No. 4,136,118). . However, dimethyl sulfoxide and hydrogen peroxide are expensive oxidizing agents compared to atmospheric oxygen and sulfur.
Ebenso ist die Verwendung von Schwefel zur Herstellung von aliphatischen Disulfiden aus Mercaptanen bekannt, wobei in Gegenwart von Basen wie Alkalihydroxiden oder tertiären aliphatischen Aminen, und in Gegenwart von Alkoholen als Lösungsmittel (US-PS 3 340 324), N-Methylpyrrolidon oder Isopropanol. gegebenenfalls im Gemisch mit Wasser, als Lösungsmittel (US-PS 3 994 979) oder in aliphatischen Disulfiden als Lösungsmittel (DE-AS 1 214 220) gearbeitet wird.Likewise, the use of sulfur for the production of aliphatic disulfides from mercaptans is known, in the presence of bases such as alkali hydroxides or tertiary aliphatic amines, and in the presence of alcohols as solvents (US Pat. No. 3,340,324), N-methylpyrrolidone or isopropanol. optionally in a mixture with water, as a solvent (US Pat. No. 3,994,979) or in aliphatic disulfides as a solvent (DE-AS 1 214 220).
Es wurde nun ein Verfahren zur Herstellung von Bis-(aminophenyl)-disulfiden der Formel
- R für Wasserstoff oder Halogen steht,
das dadurch gekennzeichnet ist, daß man Amino-thiophenole der Formel
- R die oben angegebene Bedeutung hat,
mit Schwefel oder einer schwefelabgebenden Substanz in wäßriger Dispersion bei einer Temperatur
von 10 bis 120°C und einem pH-Wert von 3 bis 9 umsetzt.There has now been a process for the preparation of bis (aminophenyl) disulfides of the formula
- R represents hydrogen or halogen,
which is characterized in that amino-thiophenols of the formula - R has the meaning given above,
with sulfur or a sulfur-donating substance in aqueous dispersion at one temperature
from 10 to 120 ° C and a pH of 3 to 9.
Als Halogen sei beispielsweise Fluor, Chlor, Brom, Jod, bevorzugt Chlor oder Brom, besonders bevorzugt Chlor, genannt.Halogen is, for example, fluorine, chlorine, bromine, iodine, preferably chlorine or bromine, particularly preferably chlorine.
Das erfindungsgemäße Verfahren kann am Beispiel der Umsetzung von 2-Amino-thiophenol und Schwefel durch die folgende Formelgleichung wiedergegeben werden;
Als Amino-thiophenol für das erfindungsgemäße Verfahren seien beispielsweise genannt:
- 2-Amino-thiophenol, 4-Amino-thiophenol, 2-Chlor-4-amino-thiophenol,
- 2-Brom-4-amino-thiophenol, 4-Chlor-2-amino-thiophenol,
- 4-Brom-2-amino-thiophenol, 3-Chlor-2-amino-thiophenol,
- 6-Chlor-2-amino-thiophenol und 3-Chlor-4-amino-thiophenol.
- 2-amino-thiophenol, 4-amino-thiophenol, 2-chloro-4-amino-thiophenol,
- 2-bromo-4-aminothiophenol, 4-chloro-2-aminothiophenol,
- 4-bromo-2-aminothiophenol, 3-chloro-2-aminothiophenol,
- 6-chloro-2-aminothiophenol and 3-chloro-4-aminothiophenol.
Bevorzugte Amino-thiophenole für das erfindungsgemäße Verfahren sind solche in denen R für Wasserstoff oder Chlor steht.Preferred amino-thiophenols for the process according to the invention are those in which R represents hydrogen or chlorine.
Besonders bevorzugt für das erfindungsgemäße Verfahren ist der Einsatz von 2-Amino-thiophenol.The use of 2-amino-thiophenol is particularly preferred for the process according to the invention.
Amino-thiophenole sind bekannte Verbindungen und können nach bekannten Verfahren, beispielsweise durch Umsetzung von Chlor-nitro-benzolen mit Hydrogensulfiden oder Sulfiden hergestellt werden (DE-OS 2 127 898).Amino-thiophenols are known compounds and can be prepared by known processes, for example by reacting chloro-nitro-benzenes with hydrogen sulfides or sulfides (DE-OS 2 127 898).
Die Amino-thiophenole werden im erfindungsgemäßen Verfahren mit Schwefel umgesetzt. Der Schwefel kann hierbei in Form von elementaren Schwefel, wie Schwefelpulver, Schwefelschuppen, Schwefelblume, oder über eine schwefelabgebende Substanz im erfindungsgemäßen Verfahren eingesetzt werden Als schwefelabgebende Substanzen seien Polysulfide, wie Disulfide oder Trisulfide, und Thiosulfate, wie Natriumthiosulfat oder die beim Ansäuern freigesetzte Thioschwefelsäure (Gmelins Handbuch der anorganischen Chemie, 8. Auflage, Band 9, Seite 874 Verlag Chemie 1960) genannt.The amino-thiophenols are reacted with sulfur in the process according to the invention. The sulfur can be used in the form of elemental sulfur, such as sulfur powder, sulfur scales, sulfur flower, or via a sulfur-releasing substance in the process according to the invention. Gmelin's handbook of inorganic chemistry, 8th edition, volume 9, page 874 Verlag Chemie 1960).
Schwefel oder die schwefelabgebende Substanz werden zweckmäßigerweise im erfindungsgemäßen Verfahren in einer solchen Menge eingesetzt, daß pro Mol Amino-thiophenol 0,4 bis 0,7 Mol, vorzugsweise 0,5 bis 0,55 Mol, Schwefel vorhanden ist.Sulfur or the sulfur-releasing substance is expediently used in the process according to the invention in an amount such that 0.4 to 0.7 mol, preferably 0.5 to 0.55 mol, of sulfur is present per mol of aminothiophenol.
Das erfindungsgemäße Verfahren wird bei einer Temperatur von 10 bis 120°C, bevorzugt 50 bis 110°C, durchgeführt. Besonders bevorzugt wird bei Rückflußtemperatur des Reaktionsgemisches gearbeitet.The process according to the invention is carried out at a temperature of 10 to 120 ° C., preferably 50 to 110 ° C. It is particularly preferred to work at the reflux temperature of the reaction mixture.
Das erfindungsgemäße Verfahren wird in der Regel bei einem Druck zwischen 0,01 und 1 bar, bevorzugt 0,5 und 1 bar durchgeführt. Besonders bevorzugt wird bei Normaldruck gearbeitet. Der pH-Wert für die Durchführung des erfindungsgemäßen Verfahrens kann im Bereich von 3 bis 9, vorzugsweise im Bereich von 4 bis 8 liegen. Bei der Verwendung von salzartigen schwefelabgebenden Substanzen, wie Natriumthiosulfat, und/oder beim Einsatz der Aminothiophenole in Form ihrer Salze wird der pH-Wert durch Zugabe einer kleinen Menge einer Mineralsäure oder organischen Säure eingestellt. Bei der Umsetzung von Amino-thiophenolen mit Schwefel stellt sich im allgemeinen der erforderliche pH-Wert ohne weitere Hilfsstoffe ein. Für den Fall, daß zur pH-Einstellung eine Säure verwandt wird, sei beispielsweise eine starke Mineralsäure, wie Salzsäure oder Schwefelsäure, eine schwache Mineralsäure, wie z. B. Kohlensäure (Kohlendioxid in Wasser) oder eine organische Säure, wie Essigsäure oder Ameisensäure, genannt.The process according to the invention is generally carried out at a pressure between 0.01 and 1 bar, preferably 0.5 and 1 bar. Working at normal pressure is particularly preferred. The pH for carrying out the process according to the invention can be in the range from 3 to 9, preferably in the range from 4 to 8. When using salt-like sulfur-releasing substances, such as sodium thiosulfate, and / or when using the aminothiophenols in the form of their salts, the pH is adjusted by adding a small amount of a mineral acid or organic acid. When amino-thiophenols are reacted with sulfur, the required pH is generally established without further auxiliaries. In the event that an acid is used to adjust the pH, be for example a strong mineral acid such as hydrochloric acid or sulfuric acid, a weak mineral acid such as e.g. B. carbonic acid (carbon dioxide in water) or an organic acid such as acetic acid or formic acid.
Zur Durchführung des erfindungsgemäßen Verfahrens werden die Ausgangskomponenten bei Raumtemperatur in Wasser dispergiert und dann unter Rühren auf die Reaktionstemperatur erhitzt, wobei der bei der Umsetzung gebildete Schwefelwasserstoff entweicht. Der Schwefelwasserstoff wird nach üblichen Methoden isoliert oder umgewandelt, beispielsweise durch Absorption in Alkalihydroxidlösungen und Umwandlung in das zugehörige Alkalisalz oder durch Oxidation zu Schwefel. Gegen Ende der Umsetzung wird zur weitgehenden Entfernung des restlichen Schwefelwasserstoffs ein schwaches Vakuum an das Reaktionsgemisch gelegt oder ein Trägergasstrom, beispielsweise Stickstoff oder Luft, durch die Reaktionsmischung geleitet. Nach der Abkühlung des Reaktionsgemisches, beispielsweise auf eine Temperatur zwischen 0 und 20°C, kann das Produkt in üblicher Weise, beispielsweise durch Filtrieren, Absaugen oder Abschleudern isoliert werden.To carry out the process according to the invention, the starting components are dispersed in water at room temperature and then heated to the reaction temperature with stirring, the hydrogen sulfide formed during the reaction escaping. The hydrogen sulfide is isolated or converted by customary methods, for example by absorption in alkali metal hydroxide solutions and conversion into the associated alkali metal salt or by oxidation to sulfur. Towards the end of the reaction, a slight vacuum is applied to the reaction mixture or a carrier gas stream, for example nitrogen or air, is passed through the reaction mixture to largely remove the remaining hydrogen sulfide. After the reaction mixture has cooled, for example to a temperature between 0 and 20.degree. C., the product can be isolated in a conventional manner, for example by filtration, suction or centrifuging.
Überraschenderweise werden die Bis-(amino-phenyl)-disulfide nach dem erfindungsgemäßen Verfahren in praktisch quantitativen Ausbeuten und in hoher Reinheit erhalten, während nach den Verfahren des Standes der Technik stets mehr oder weniger stark verunreinigte Produkte anfallen. Die nach dem erfindungsgemäßen Verfahren herstellbaren Bis-(amino-phenyl)-disulfide können als Fungizide, Beizmittel für Epoxidharze, Komponenten für Schmieröl-Additive, Komponenten für Polyurethan-Präpolymere, Kautschukpeptisierungsmittel und als Zwischenprodukte für die Synthese von Benzthiazolderivaten verwendet werden (DE-US 2 503 164).Surprisingly, the bis (aminophenyl) disulfides are obtained by the process according to the invention in practically quantitative yields and in high purity, while the processes according to the prior art always produce more or less highly contaminated products. The bis- (aminophenyl) disulfides which can be prepared by the process according to the invention can be used as fungicides, mordants for epoxy resins, components for lubricating oil additives, components for polyurethane prepolymers, rubber peptizers and as intermediates for the synthesis of benzothiazole derivatives (DE-US 2 503 164).
25 g (0,2 Mol) 2-Amino-thiophenol und 3,5 g (0,11 Mol) Schwefel werden in 150 ml Wasser dispergiert und die Mischung wird 90 Minuten lang unter Rückfluß zum Sieden erhitzt und gerührt. Nach Abkühlen auf 20°C wird abgesaugt und das Produkt bei 40°C im Wasserstrahlvakuum getrocknet. Ausbeute 25g g (100% der theoretischen Ausbeute); Schmelzpunkt 93°C. Nach dünnschichtchromatographischer Kontrolle (Methylenchlorid an Kieselgel) ist das Produkt einheitlich Bis-(2-amino-phenyl)-disulfid.25 g (0.2 mol) of 2-amino-thiophenol and 3.5 g (0.11 mol) of sulfur are dispersed in 150 ml of water and the mixture is refluxed for 90 minutes and stirred. After cooling to 20 ° C is suctioned off and the product is dried at 40 ° C in a water jet vacuum. Yield 25 g (100% of the theoretical yield); Melting point 93 ° C. After checking by thin layer chromatography (methylene chloride on silica gel), the product is bis (2-aminophenyl) disulfide.
25 g (0,2 Mol) 2-Amino-thiophenol und 25 g (0,1 Mol) Natriumthiosulfat-pentahydrat werden in 150 ml Wasser vorgelegt und die Mischung wird 2 Stunden lang unter Rückfluß erhitzt und gerührt. Nach Abkühlen auf 20°C wird abgesaugt und das Produkt bei 40° C im Wasserstrahlvakuum getrocknet.25 g (0.2 mol) of 2-amino-thiophenol and 25 g (0.1 mol) of sodium thiosulfate pentahydrate are placed in 150 ml of water and the mixture is heated under reflux and stirred for 2 hours. After cooling to 20 ° C is suctioned off and the product is dried at 40 ° C in a water jet vacuum.
Ausbeute: 20,5 g (82% der theoretischen Ausbeute) Bis-(2-amino-phenyl)-disulfid; Schmelzpunkt 93° C.Yield: 20.5 g (82% of the theoretical yield) bis (2-aminophenyl) disulfide; Melting point 93 ° C.
Der Versuch wird wie in Beispiel 2 beschrieben durchgeführt mit der Abweichung, daß bei ca. 80° C durch Zutropfen von Essigsäure der pH-Wert auf 5 eingestellt wird.The experiment is carried out as described in Example 2, with the difference that the pH is adjusted to 5 at about 80 ° C. by the dropwise addition of acetic acid.
Ausbeute: 24,5 g (98% der Theorie) Bis-(2-amino-phenyl)-disulfid; Schmelzpunkt 93° C.Yield: 24.5 g (98% of theory) bis (2-aminophenyl) disulfide; Melting point 93 ° C.
Der Versuch wird wie im Beispiel 2 beschrieben durchgeführt mit der Abweichung, daß bei ca. 80° C Kohlendioxid eingeleitet wird und durch Zutropfen von 40%iger Schwefelsäure der pH-Wert auf 5 eingestellt wird.The experiment is carried out as described in Example 2, with the difference that carbon dioxide is introduced at about 80 ° C. and the pH is adjusted to 5 by dropwise addition of 40% strength sulfuric acid.
Ausbeute: 24,5 g (98% der Theorie) Bis-(2-amino-phenyl)-disulfid; Schmelzpunkt 93° C.Yield: 24.5 g (98% of theory) bis (2-aminophenyl) disulfide; Melting point 93 ° C.
Claims (10)
characterised in that amino-thiophenols of the formula
are reacted with sulphur or a sulphur-donating substance in aqueous dispersion at a temperature of 10 to 120°C and a pH value of 3 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803009846 DE3009846A1 (en) | 1980-03-14 | 1980-03-14 | METHOD FOR PRODUCING BIS (AMINO-PHENYL) DISULFIDES |
| DE3009846 | 1980-03-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0036120A1 EP0036120A1 (en) | 1981-09-23 |
| EP0036120B1 true EP0036120B1 (en) | 1983-02-09 |
Family
ID=6097229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81101477A Expired EP0036120B1 (en) | 1980-03-14 | 1981-03-02 | Process for the production of bis-(amino-phenyl) disulphides |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4375562A (en) |
| EP (1) | EP0036120B1 (en) |
| JP (1) | JPS56142258A (en) |
| DE (2) | DE3009846A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4342619A1 (en) * | 1993-12-14 | 1995-06-22 | Bayer Ag | Improved process for the preparation of 2,2'-dinitrodiphenyl disulfide |
| DE69911737T2 (en) * | 1998-09-09 | 2004-08-12 | Nippon Finechemical Co., Ltd. | METHOD FOR PRODUCING AROMATIC SULFUR COMPOUNDS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA462497A (en) * | 1950-01-17 | Timothy Paul Philip | Manufacture of dithio bis-arylamine | |
| US1933217A (en) * | 1930-08-01 | 1933-10-31 | Matieres Colorantes & Prod Chi | Manufacture of diaminodiphenyldisulphides |
| US2435508A (en) * | 1944-11-01 | 1948-02-03 | Us Rubber Co | Manufacture of dithio bisarylamines |
-
1980
- 1980-03-14 DE DE19803009846 patent/DE3009846A1/en not_active Withdrawn
-
1981
- 1981-02-26 US US06/238,348 patent/US4375562A/en not_active Expired - Fee Related
- 1981-03-02 DE DE8181101477T patent/DE3160052D1/en not_active Expired
- 1981-03-02 EP EP81101477A patent/EP0036120B1/en not_active Expired
- 1981-03-11 JP JP3404781A patent/JPS56142258A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0036120A1 (en) | 1981-09-23 |
| US4375562A (en) | 1983-03-01 |
| DE3160052D1 (en) | 1983-03-17 |
| DE3009846A1 (en) | 1981-09-24 |
| JPS56142258A (en) | 1981-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0131776B1 (en) | Process for the preparation of thiazole-2-sulfenamides | |
| EP0051202B1 (en) | Process for preparing 2,3-dichloro-sulfonyl acrylonitriles | |
| EP0187349A2 (en) | Process for the preparation of 1,2-benzisothiazolones | |
| EP0036120B1 (en) | Process for the production of bis-(amino-phenyl) disulphides | |
| DE1012914B (en) | Process for the preparation of benzthiazolyl-2-sulfenemorpholide | |
| EP0057889B1 (en) | Process for preparing 1-alkyl-2-chloro-5-nitro-benzene-4-sulphonic acids | |
| EP0180650B1 (en) | Process for the preparation of thiurane polysulphides | |
| EP0003141B1 (en) | Process for the preparation of 2-amino-arylenothiazole compounds and their ring n-substituted derivatives | |
| EP0481366A1 (en) | Process for the preparation of 2-Aminodithiothiazoles and 2-Aminotrithiothiazoles | |
| EP0019700B1 (en) | Process for the preparation of phosphorchloride thiolates | |
| DE69118175T2 (en) | NEW DISULFID DERIVATIVE | |
| DE3111518C2 (en) | Process for the preparation of carbamoylsulfonic acid salts | |
| EP0179931B1 (en) | Process for the preparation of thiuram polysulphides | |
| EP0011794B1 (en) | Process for the production of sulfamic acid halides | |
| EP0111120B1 (en) | Process for the preparation of anthraquinones | |
| DE2716897C3 (en) | Process for the preparation of N, N'-diphenylthioureas | |
| EP0008055A1 (en) | Process for the preparation of dimethyldiphenylthiuram disulphide | |
| EP0202493A1 (en) | Process for the preparation of 5-fluorotoluene-2,4-disulfochloride | |
| DE2127898B2 (en) | PROCESS FOR THE PREPARATION OF INERT-SUBSTITUTED O- AND P-AMINOTHIOPHENOLS, IF NECESSARY | |
| DE10394213B4 (en) | Process for the synthesis of bis (4-substituted quinolyl) disulphides | |
| AT239243B (en) | Process for the preparation of 2, 3-dicyano-1, 4-dithia-anthrahydroquinone and -anthraquinone | |
| EP0039905A1 (en) | Process for the preparation of 2-chloro-benzothiazole | |
| EP0255678A1 (en) | Process for production of benzoyl ureas | |
| DE1933242A1 (en) | Process for the production of trichloromethanthiosulfenyl chloride multistage lubricating pumps | |
| DE2709990A1 (en) | PROCESS FOR THE PREPARATION OF 2-MERCAPTOBENZOTHIAZOLE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19810306 |
|
| AK | Designated contracting states |
Designated state(s): BE DE FR GB |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): BE DE FR GB |
|
| REF | Corresponds to: |
Ref document number: 3160052 Country of ref document: DE Date of ref document: 19830317 |
|
| ET | Fr: translation filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19840223 Year of fee payment: 4 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19840301 Year of fee payment: 4 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19840331 Year of fee payment: 4 |
|
| BERE | Be: lapsed |
Owner name: BAYER A.G. Effective date: 19880331 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19881118 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19881130 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19881201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19890331 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |